12-membered Ring Channels Research Articles

Designable Synthesis of Layered Silicates and Tunable Interlayer Expanded to Zeolites.

Layered zeolitic silicates and corresponding interlayer-expanded porous materials exhibit attractive application potential in wide fields. Nonetheless, designable synthesis and structure analysis of layered silicates remain challenging. Herein, two kinds of layered silicates are synthesized using different di-quaternary ammonium-type organic structure-directing agents (OSDAs). Their crystal structures are analyzed and verified by 3D electron diffraction (3D ED) and high-resolution TEM imaging. The suitable configurations of OSDA can lead to desirable interlayer states. Additionally, two new zeolite structures both with 12-membered ring (MR) channels intersected by 8 MR channels and larger interlayer spaces are constructed from layered silicate precursors by interlayer silylation. The new zeolitic material exhibits potential application in adsorption of organic pollution and catalytic reaction. This study is expected to develop versatile ways for the design and synthesis of layered silicates even zeolites and provide references in characterizing layered materials and zeolites as well.

Relay Catalysis for Highly Selective Conversion of Methanol to Ethylene in Syngas.

The precise C-C coupling is a challenging goal in C1 chemistry. The conversion of methanol, a cheap and easily available C1 feedstock, into value-added and largely demanded olefins has been playing a game-changing role in the production of olefins. The current methanol-to-olefin (MTO) process, however, suffers from limited selectivity to a specific olefin. Here, we present a relay-catalysis route for the high-selective conversion of methanol to ethylene in syngas (H2/CO) typically used for methanol synthesis. A bifunctional catalyst composed of selectively dealuminated H-MOR zeolite and ZnO-TiO2, which implemented methanol carbonylation with CO to acetic acid and selective acetic acid hydrogenation to ethylene in tandem, offered ethylene selectivity of 85% at complete methanol conversion at 583 K. The selective removal of Brønsted acid sites in the 12-membered ring channel of H-MOR favors the selectivity of acetic acid in CH3OH carbonylation. The high capabilities of ZnO-TiO2 in the adsorption of acetic acid and the activation of H2 play key roles in selective hydrogenation of acetic acid to ethylene. Our work provides a promising relay-catalysis strategy for precise C-C coupling of C1 to C2 molecules.

Enhancement of the dimethyl ether carbonylation activation via regulating acid sites distribution in FER zeolite framework

The carbonylation of dimethyl ether (DME) with CO is a key step for ethanol synthesis from syngas, but traditional mordenite (MOR) zeolite shows low catalytic stability. Herein, various FER zeolite nanosheets were prepared with four types of organic templates. The catalytic performance of FER in DME carbonylation is strongly dependent on the location of strong acid site in framework, which can be effectively regulated by altering organic template. FER-MORP sample synthesized with morpholine shows the highest DME conversion of 53%, thus, giving a methyl acetate space-time yield (STYMA) of 0.889mmol g-1 h-1. DFT calculation, NH3-IR, 1H/27Al/29Si MAS NMR, and in situ DRIFTS results indicate that morpholine directs more Al species, or strong Brønsted acid sites (BAS), to locate in 8-membered ring (8-MR) channels, which not only enhances carbonylation activity but also suppresses formation of coke species. The catalytic performance is well maintained within 4 repeated recycles (∼460 h).

Location of Brønsted sites in deuterated L-zeolite: A combined neutron powder diffraction and computer modeling study

In this work both concentration and location of Brønsted acid sites (BASs) in a deuterated L-zeolite were determined by combining neutron powder diffraction with ab-initio molecular dynamics modelling. From the structure refinement of the acidic L zeolite, two Brønsted acid sites were identified. The first one, D1, is on the framework oxygen O5 pointing toward the center of the 8-membered ring channel; the second one, D2, located in proximity of the framework oxygen O1 pointing toward the 12-membered ring channel running parallel to the c-axis. On the whole, ∼7.7 acid sites were located in the unit-cell, corresponding to 58% and 14% for D1 and D2, respectively. The average structure of the simulated D-LTL was in good agreement with the experimental structure. The modelling revealed that the D2 BAS shows a large degree of mobility, consistent with the high thermal factor associated with that atomic position. The D1 BAS showed a behaviour consistent with static disorder, while the D2 BAS was characterized by a significant degree of dynamical disorder. In addition to these findings, the study also revealed that the O1 BAS had a higher Brønsted base character compared to the average basicity of the framework oxygens of the 12-membered ring channels.

Activity Enhancement of Ferrierite in Dimethyl Ether Carbonylation Reactions through Recrystallization with Sodium Oleate.

Methyl acetate (MA) has a wide range of applications as an important industrial chemical. Traditional MOR zeolite for carbonylation of DME to MA accumulated carbon easily because of a 12-membered ring (12 MR) channel. In this work, we innovatively developed the method of recrystallization ferrierite (FER) zeolite using special chelating ligand sodium oleate which can affect ions other than alkali metals. The characterization results of N2 adsorption, transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR) show that hydrothermal recrystallization of ferrierite using sodium oleate resulted in a higher Si/Al ratio, a bigger specific surface area and a larger number of Brønsted acid sites in the eight MR channels, which was more efficient in the reaction of carbonylation of dimethyl ether than ordinary alkali treatment.

Two Carboxylate-Cyanurates with Strong Optical Anisotropy and Large Band Gaps.

The first metal carboxylate-cyanurates, namely, K(H3C3N3O3)(HCO2) (I) and Ba2(H2C3N3O3)(CH3CO2)3(H2O) (II), which contain π-conjugated carboxylate and cyanurate groups, have been synthesized by hydrothermal methods. They crystallize in centrosymmetric space groups of P1̅ and P21/n, respectively. Compound I exhibits a novel three-dimensional (3D) structure based on a [K(H3C3N3O3)]+ cationic framework with 12-membered ring (12-MR) channels, and the (HCO2)- anions are located within the 12-MR channels. The [K(H3C3N3O3)]+ cationic framework is composed of K+ ions interconnected by H3C3N3O3 ligands. Compound II features a 3D network formed by [Ba2(CH3CO2)3]+ cationic double chains bridged by (H2C3N3O3)- anions. The [Ba2(CH3CO2)3]+ cationic double chain is composed of (CH3CO2)- anions and Ba2+ ions. Optical property measurements show that both compounds exhibit short ultraviolet cutoff edges (I, 208 nm; II, 218 nm) and wide band gaps (I, 5.43 eV; II, 5.20 eV). Importantly, K(H3C3N3O3)(HCO2) (I) features a large birefringence of 0.285@532 nm due to the parallel alignment of π-conjugated H3C3N3O3 and (HCO2)- groups, indicating that K(H3C3N3O3)(HCO2) (I) is a promising short-wave ultraviolet birefringent material. Detailed theoretical calculations elucidate that their excellent optical properties originate from the synergetic effect of both types of π-conjugated groups.

Improved catalytic performance in gas-phase dimethyl ether carbonylation over facile NH4F etched ferrierite.

Gas-phase dimethyl ether (DME) carbonylation to methyl acetate (MA) initiates a promising route for producing ethanol from syngas. Ferrierite (FER, ZSM-35) has received considerable attention as it displays excellent stability in the carbonylation reaction and its modification strategy is to improve its catalytic activity on the premise of maintaining its stability as much as possible. However, conventional post-treatment methods such as dealumination and desilication usually selectively remove framework Al or Si atoms, ultimately altering the intrinsic composition, crystallinity, and acidity of zeolites inevitably. In this study, we successfully prepared a series of hierarchical ZSM-35 materials through post-treatment with NH4F etching, which dissolved framework Al and Si at similar rates and preferentially attacked the defective sites. Interestingly, the produced pore systems effectively penetrated the [100] plane, offering elevated access to both the 8-membered ring (8-MR) and 10-membered ring (10-MR) channels. The physicochemical and acid properties of the pristine and NH4F etched ZSM-35 samples were comprehensively characterized using various techniques, including XRD, XRF, FESEM, HRTEM, Nitrogen adsorption-desorption, NH3-TPD, Py-IR, 27Al MAS NMR, and 29Si MAS NMR. Under moderate treatment conditions, the intrinsic microporous structure, acid properties, and crystallinity of zeolite were retained, leading to superior catalytic activity and stability with respect to the pristine sample. Nonetheless, severe NH4F etching disrupted the crystalline framework and created additional defective sites, bringing about faster deposition of coke precursors on the interior Brønsted acid sites (BAS) and decreased catalytic performance. This technique provides a novel and efficient method to slightly enhance the micropore and mesopore volume of industrially pertinent zeolites through a straightforward post-treatment, thus elevating the catalytic performance of these zeolites.

Charge-separation driven mechanism via acylium ion intermediate migration during catalytic carbonylation in mordenite zeolite

By employing ab initio molecular dynamic simulations, solid-state NMR spectroscopy, and two-dimensional correlation analysis of rapid scan Fourier transform infrared spectroscopy data, a new pathway is proposed for the formation of methyl acetate (MA) via the acylium ion (i.e.,CH3 − C ≡ O+) in 12-membered ring (MR) channel of mordenite by an integrated reaction/diffusion kinetics model, and this route is kinetically and thermodynamically more favorable than the traditional viewpoint in 8MR channel. From perspective of the complete catalytic cycle, the separation of these two reaction zones, i.e., the C-C bond coupling in 8MR channel and MA formation in 12MR channel, effectively avoids aggregation of highly active acetyl species or ketene, thereby reducing undesired carbon deposit production. The synergistic effect of different channels appears to account for the high carbonylation activity in mordenite that has thus far not been fully explained, and this paradigm may rationalize the observed catalytic activity of other reactions.

Preparation of shaped binderless mordenite catalysts with controllable crystal sizes and their carbonylation performance

A series of shaped binderless mordenite (MOR) zeolites were prepared through hydrothermal transformation with commercial MOR zeolite as seeds and aluminosilicate as raw materials. To investigate the effect of alkalinity on the crystallization process, samples with different Na2O/SiO2 ratios from 0.041 to 0.12 were synthesized and characterized by XRD, SEM, N2 adsorption-desorption, NH3-TPD, ICP-OES and pyridine adsorption-infrared measurements. It was surprisingly found that alkalinity plays a pivotal role in the formation of the binderless MOR zeolites. At Na2O/SiO2 of 0.041, MOR zeolite could not be formed. Slightly increasing the Na2O/SiO2 to 0.043 and upwards, the binderless MOR zeolite was formed. XRD patterns and SEM images revealed that the primary MOR zeolite particle size increased from 104 nm to 266 nm with the Na2O/SiO2 ratio increasing from 0.043 to 0.10. Further increasing Na2O/SiO2 ratio to 0.12 led to the formation of 0.6–1.6 μm micro-sized crystals. NH3-TPD and pyridine-adsorbed IR results indicated that the amount and strength of Brønsted acid sites in 8-membered ring channel (8-MR) decreased with the Na2O/SiO2 ratio increasing to up to 0.10. Superior catalytic performance in dimethyl ether carbonylation was observed on the catalyst with a Na2O/SiO2 ratio of 0.043, which exhibited the shortest diffusion path and highest 8-MR Brønsted acid amounts. This work provides a practical way of preparing and optimizing shaped binderless zeolites.

Selective enrichment of Brønsted acid site in 8-membered ring channels of MOR zeolite to enhance the catalytic reactivity of dimethyl ether carbonylation

Directional adjusting of the distribution of Brønsted acid site (BAS) in zeolite to control its catalytic performance is highly attractive but remains challenging. This study aims to tailor the distribution of BAS in 8-membered ring (B8-MR) of H-Mordenite (HMOR) by adding aniline or p-phenylenediamine as additives to the sol‐gel. The results reveal that the number of B8-MR is significantly increased but with a slight change in the number of BAS in 12-membered ring channels. When using dimethyl ether (DME) carbonylation as the probe reaction, the conversion of DME to methyl acetate over the synthesized HMOR zeolite is increased by nearly 2 times. Our finding not only provides a facile strategy to regulate the acid distribution in different channels of the HMOR zeolite but also offers a promising candidate for the catalytic DME carbonylation, which is a critical intermediate step for ethanol synthesis from syngas.

Dynamic Evolution of Aluminum Coordination Environments in Mordenite Zeolite and Their Role in the Dimethyl Ether (DME) Carbonylation Reaction

Part of tetrahedral framework aluminum in a protonic mordenite (HMOR) will convert geometry to distorted tetrahedral and octahedral coordination. High-field 27 Al NMR data show that more framework Al atoms at T3 and T4 sites change geometry to nonframework structures than others. These nonframework Al species preferentially reside in the side pockets, which will decrease the accessibility of acid sites in the 8-membered ring (MR) channel, impairing the dimethyl ether (DME) carbonylation reaction. The arisen octahedrally coordinated Al species are framework-associated, which can be reverted into the zeolite framework. Herein, we find that a facile treatment with pyridine could force the octahedral coordination Al back into a tetrahedral environment, which could increase the number of available active sites and enhance the diffusion of DME, thus improving the reactivity (4 times) of the DME carbonylation reaction and prolonging the lifetime of catalysts.

C(NH2)3]2Zn(CO3)2: A Guanidinium-Templated Ultraviolet Nonlinear Optical Material.

A novel guanidinium-templated ultraviolet (UV) nonlinear optical zinc carbonate crystal, [C(NH2)3]2Zn(CO3)2 (GZCO), has been synthesized in a closed system at low temperatures. GZCO crystallizing in the tetragonal noncentrosymmetric nonpolar space group, P41212 exhibits a three-dimensional anionic framework constructed by interconnected [Zn6C6O32] 12-membered ring channels with inorganic CO3 triangles and ZnO4 tetrahedra. Notably, the anhydrous GZCO shows a very high thermal stability among guanidine-based hybrid NLO materials benefiting from the confinement effect of the organic cations within inorganic channels. The UV-visible transmittance spectrum reveals that GZCO has a short UV cutoff edge of 210 nm, corresponding to the large band gap of 5.9 eV. GZCO exhibits a mild second-harmonic generation efficiency of 0.5 × KH2PO4 with type-I phase-matching behavior.

Dimethyl ether conversion to hydrocarbons on the closely interconnected FER@ZSM-5 nanostructures

A superior catalyst activity and stability for dimethyl ether (DME) conversion to gasoline-range hydrocarbons (DTG) on a novel hierarchically-structured hybridized FER@ZSM-5 were verified in terms of the strong interactions of ZSM-5 on the plate-like FER nanostructures, which were prepared by alcohol additive with two organic structure-directing agent (OSDA). The highly active nanostructured FER@ZSM-5 with a propanol additive showed the closely interconnected and highly dispersed ZSM-5 aggregates on the larger plate-like FER surfaces, which were mainly responsible for the suppressed heavy coke depositions with the help of the closely interconnected ZSM-5 and FER interfaces with abundant acidic sites on 8-membered ring (8-MR) channels. The well-dispersed ZSM-5 nanoparticles on Brønsted acid sites of FER surfaces showed coke-resistant natures for DTG reaction due to the synergy effects of the strong acidic sites of the smaller ZSM-5 particles and larger Brønsted acid sites on the plate-like FER structures. • Superior activity and stability for DTG on the hybrid FER@ZSM-5 composite were verified. • FER@ZSM-5(Propanol) with closely interconnected nanostructures showed higher stability. • Less coke deposition was observed due to closely interconnected ZSM-5 and FER interfaces.

Ultralow-temperature-driven water-based sorption refrigeration enabled by low-cost zeolite-like porous aluminophosphate

Thermally driven water-based sorption refrigeration is considered a promising strategy to realize near-zero-carbon cooling applications by addressing the urgent global climate challenge caused by conventional chlorofluorocarbon (CFC) refrigerants. However, developing cost-effective and high-performance water-sorption porous materials driven by low-temperature thermal energy is still a significant challenge. Here, we propose a zeolite-like aluminophosphate with SFO topology (EMM-8) for water-sorption-driven refrigeration. The EMM-8 is characterized by 12-membered ring channels with large accessible pore volume and exhibits high water uptake of 0.28 g·g−1 at P/P0 = 0.2, low-temperature regeneration of 65 °C, fast adsorption kinetics, remarkable hydrothermal stability, and scalable fabrication. Importantly, the water-sorption-based chiller with EMM-8 shows the potential of achieving a record coefficient of performance (COP) of 0.85 at an ultralow-driven temperature of 63 °C. The working performance makes EMM-8 a practical alternative to realize high-efficient ultra-low-temperature-driven refrigeration.

Preparation of core-shell ZSM-5@Beta molecular sieve and catalytic alkylation to 2,6-Dimethylnaphthalene

ZSM-5@Beta core-shell molecular sieve was prepared by dynamic hydrothermal synthesis method using ZSM-5 adhered Beta seed crystals as the core phase, and polydiallyl dimethyl ammonium chloride (PDDA) was used as a coupling agent to adhere Beta seed crystals on the surface of ZSM-5. The structure and physical properties of composite molecular sieves were characterized by XRD, N2 adsorption-desorption, SEM, TEM, ICP, NH3-TPD and Py-FTIR. The catalytic performance of composite molecular sieves for alkylation of 2-methylnaphthalene (2-MN) with methanol was investigated. The results showed that ZSM-5@Beta composite molecular sieve prepared by this method had a core-shell structure, and the particle size was about 500 nm. Compared with mechanically mixed binary molecular sieve, core-shell molecular sieve had higher specific surface area and external surface area, lower acid strength and stronger acid center density. Through the construction of core-shell interface and hierarchical porous, the catalytic activity was improved by shell phase Beta molecular sieve with 12-membered ring channel, and the catalytic selectivity was improved by core phase ZSM-5 molecular sieve with 10-membered ring channel in the alkylation reaction of 2-MN with methanol. The 2,6-/2,7-DMN ratio in the products reached 1.35, and the yield of 2,6-DMN reached 4.29%.

Ce-exchange capacity of zeolite L in different cationic forms: a structural investigation

Cerium exchange by microporous materials, such as zeolites, has important applications in different fields, for example, rare earth element recovery from waste or catalytic processes. This work investigated the Ce-exchange capacity of zeolite L in three different cationic forms (the as-synthesized K form and Na- and NH4-exchanged ones) from a highly concentrated solution. Chemical analyses and structural investigations allowed determination of the mechanisms involved in the exchanges and give new insights into the interactions occurring between the cations and the zeolite framework. Different cation sites are involved: (i) K present in the original LTL in the cancrinite cage (site KB) cannot be exchanged; (ii) the cations in KD (in the 12-membered ring channel) are always exchanged; while (iii) site KC (in the eight-membered ring channel) is involved only when K+ is substituted by NH4 +, thus promoting a higher exchange rate for NH4 + → K+ than for Na+ → K+. In the Ce-exchanged samples, a new site occupied by Ce appears in the centre of the main channel, accompanied by an increase in the number of and a rearrangement of H2O molecules. In terms of Ce exchange, the three cationic forms behave similarly, from both the chemical and structural point of view (exchanged Ce ranges from 38 to 42% of the pristine cation amount). Beyond the intrinsic structural properties of the zeolite L framework, the Ce exchange seems thus also governed by the water coordination sphere of the cation. Complete Ce recovery from zeolite pores was achieved.

Effect of N-Methyl-2-pyrrolidone on Al Distribution in MOR and Enhanced Activity in DME Carbonylation Reaction

A biased acid site distribution in mordenite (MOR), which refers to the enrichment of acid sites within 8-membered ring (MR) channels, was observed with the addition of N-methyl-2-pyrrolidone (NMP) in the initial gel and verified by the enhanced activity in dimethyl ether (DME) carbonylation reaction. This is the first time that lactam has been proved effective in regulating acid site distribution, and the possible mechanism was investigated.

Comparative study on the catalytic performance of zeolite catalysts with different topologies in 1-methylnaphthalene isomerization-transalkylation coupling reaction

The isomerization-transalkylation coupling reaction between 2-methylnaphthalene and dimethylnaphthalene was studied over zeolite catalysts to produce them. The catalytic performance of zeolites with MWW, BEA, FAU and MFI topological structure was investigated and the reaction mechanism was discussed. The properties of zeolites were characterized by XRD, N2 adsorption-desorption, SEM, NH3-TPD, Py-FTIR and ICP. Compared with MFI zeolite with 10-membered ring channel, MWW, BEA and FAU zeolite with 12-membered ring channel showed better catalytic activity. BEA zeolite exhibited higher selectivity to dimethylnaphthalene, while MWW zeolites showed higher selectivity to 2-methylnaphthalene and the best catalytic stability. As a branch of MWW zeolites, HMCM-22 showed a 1-methylnaphthalene conversion of 70.27% and a 2-methylnaphthalene yield of 66.69%. It was worth noting that a relatively high yield of 2-methylnaphthalene (35.74%) and dimethylnaphthalene (19.00%) were obtained on HMCM-56 at the same time. This research has opened up a promising route using C10 aromatics as raw materials for the preparation of 2,6-dimethylnaphthalene, an important polyester monomer.

Extra-Large Pore Titanosilicate Synthesized via Reversible 3D–2D–3D Structural Transformation as Highly Active Catalyst for Cycloalkene Epoxidation

Titanosilicates with extra-large pores or cages are expected to effectively release the diffusion constraints suffered by the bulky substrates in the hydrogen peroxide-involved liquid-phase selective oxidation reactions. A reversible 3D–2D–3D structural transformation was developed to fabricate a highly active IWV-type titanosilicate (Ti-IWV) with a two-dimensional intersecting 12-membered ring (MR) channel system and extra-large 14-MR supercages. The IWV germanosilicate was readily disassembled into a layered 2D material (Hydro-IWV) in HNO3 aqueous solution, which was reconstructed to Ti-IWV with various Ti contents (Si/Ti ratio of 40–∞) through the (NH4)2TiF6-assisted isomorphous substitution of Ti and structure repair. The fluoride anions were critical to recover the interlayer double-four-ring (d4r) units, which were destroyed in the hydrolysis process. Ti-IWV was extremely active in the liquid-phase epoxidation reaction of cycloalkenes, especially showing a much higher conversion (99%) for cyclooctene than conventional titanosilicates. Rather than diffusion rate, the high capacity for the adsorption of bulky alkene molecules of extra-large 14-MR cages contributed to the outstanding activity of Ti-IWV.

Silver-Modified Nano Mordenite for Carbonylation of Dimethyl Ether

Mordenite (H-MOR) catalysts were synthesized by a hydrothermal method, and silver-modified mordenite (Ag-MOR) catalysts were prepared by ion exchange with AgNO3 at different concentrations. The performance of these catalysts in the carbonylation of dimethyl ether (DME) to methyl acetate (MA) was also evaluated. The catalysts were characterized by Ar adsorption/desorption, XRD, ICP-AES, SEM, HRTEM, 27Al NMR, H2-TPR, NH3-TPD, Py-IR, and CO-TPD. According to the characterization results, Ag ion exchange sites were mainly located in the 8-membered ring (8-MR) channels of Ag-MOR; evenly dispersed Ag2O particles were also present. The acid site distribution was changed by the modification of Ag, and the amount of Brønsted acid sites increased in 8-MR and decreased in 12-MR. The CO adsorption performance of the catalyst significantly increased with the modification of Ag. These changes improved the conversion and selectivity of the carbonylation of DME. Over 4Ag-MOR in particular, DME conversion and MA selectivity reached 94% and 100%, respectively.